Radical cyclisation onto nitriles

被引：52

作者：

Bowman, WR ^{[1
]}

Bridge, CF ^{[1
]}

Brookes, P ^{[1
]}

机构：

[1] Univ Loughborough, Dept Chem, Loughborough LE11 3TU, Leics, England

来源：

TETRAHEDRON LETTERS | 2000年 / 41卷 / 46期

基金：

英国工程与自然科学研究理事会;

关键词：

radical cyclisation; nitriles; iminyl radicals; beta-scission;

D O I：

10.1016/S0040-4039(00)01596-3

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Iminyl radicals, generated by 5-exo cyclisation of alkyl, vinyl and aryl C-centred radicals onto nitriles, undergo beta -scission (nitrile translocation), reduction or tandem cyclisation onto alkenes depending on the nature of the alpha -substituent. 5-exo Cyclisations of aryl radicals onto nitriles undergo nitrile translocation when the alpha -substituent is CN, CO2R, SO2Ph or CONMe2. The rate of translocation is faster than 5- or 6-exo cyclisation onto alkenes or 1,5-hydrogen abstraction of allylic hydrogens. When the alpha -substituents are alkyl, the intermediate iminyl radicals do not undergo nitrile translocation. (C) 2000 Elsevier Science Ltd. All rights reserved.

引用

页码：8989 / 8994

页数：6

共 32 条

[1] CARBOHYDRATES TO CARBOCYCLES - SYNTHESIS OF THE DENSELY FUNCTIONALIZED CARBOCYCLIC CORE OF TETRODOTOXIN BY RADICAL CYCLIZATION OF AN ANHYDRO SUGAR PRECURSOR [J].

ALONSO, RA ;

BURGEY, CS ;

RAO, BV ;

VITE, GD ;

VOLLERTHUN, R ;

ZOTTOLA, MA ;

FRASERREID, B .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (15) :6666-6672

[2] REARRANGEMENT OF SUITABLY CONSTITUTED ARYL, ALKYL, OR VINYL RADICALS BY ACYL OR CYANO GROUP MIGRATION [J].

BECKWITH, ALJ ;

OSHEA, DM ;

WESTWOOD, SW .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (08) :2565-2575

[3] CYANO OR ACYL GROUP MIGRATION BY CONSECUTIVE HOMOLYTIC ADDITION AND BETA-FISSION [J].

BECKWITH, ALJ ;

OSHEA, DM ;

GERBA, S ;

WESTWOOD, SW .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1987, (09) :666-667

[4] Intramolecular Addition In Hex-5-enyl, Hept-6-enyl, and Oct-7-enyl Radicals [J].

Beckwith, Athelstan L. J. ;

Moad, Graeme .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1974, (12) :472-473

[5] IMINYL RADICALS .2. RING-OPENING OF CYCLOBUTYL- AND CYCLOPENTYLIMINYL RADICALS [J].

BOIVIN, J ;

FOUQUET, E ;

ZARD, SZ .

TETRAHEDRON, 1994, 50 (06) :1757-1768

[6] IMINYL, AMIDYL, AND CARBAMYL RADICALS FROM O-BENZOYL OXIMES AND O-BENZOYL HYDROXAMIC ACID-DERIVATIVES [J].

BOIVIN, J ;

CALLIERDUBLANCHET, AC ;

QUICLETSIRE, B ;

SCHIANO, AM ;

ZARD, SZ .

TETRAHEDRON, 1995, 51 (23) :6517-6528

[7] AMIDYL AND CARBAMYL RADICALS BY STANNANE MEDIATED CLEAVAGE OF O-BENZOYL HYDROXAMIC ACID-DERIVATIVES [J].

CALLIER, AC ;

QUICLETSIRE, B ;

ZARD, SZ .

TETRAHEDRON LETTERS, 1994, 35 (33) :6109-6112

[8] Iminyl radical generation via iminodithiocarbonate group transfer [J].

CallierDublanchet, AC ;

QuicletSire, B ;

Zard, SZ .

TETRAHEDRON LETTERS, 1997, 38 (14) :2463-2466

[9] Radical annulations with nitriles: Novel cascade reactions of cyano-substituted alkyl and sulfanyl radicals with isonitriles [J].

Camaggi, CM ;

Leardini, R ;

Nanni, D ;

Zanardi, G .

TETRAHEDRON, 1998, 54 (21) :5587-5598

[10] OBSERVATIONS REGARDING DELTA-CYANO AND EPSILON-CYANO RADICAL CYCLIZATIONS [J].

CHENERA, B ;

CHUANG, CP ;

HART, DJ ;

HSU, LY .

JOURNAL OF ORGANIC CHEMISTRY, 1985, 50 (25) :5409-5410

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